Triazine derivatives and their use as sunscreens

ABSTRACT

There are described triazine derivatives of formula (1), wherein R 1  is an unsubstituted or mono- or poly-hydroxy-, C 1 -C 18  alkyl-, C 1 -C 18  alkoxy-, amino-, C 1 -C 5  monoalkylamino- or di-C 1 -C 5  alkylamino-substituted C 1 -C 18  alkyl, C 2 -C 18  alkenyl, C 6 -C 10  aryl or C 6 -C 10  heteroaryl radical; unsubstituted or C 1 -C 5  alkyl-substituted C 5 -C 7  cycloalkyl or C 5 -C 7  cycloalkenyl; —OR′; or —NR′R″; R 2  is hydrogen; an unsubstituted or mono- or poly-hydroxy-, C 1 -C 18  alkoxy-, cyano-, amino, C 1 -C 5  monoalkylamino- or di-C 1 -C 5  alkylamino-substituted C 1 -C 18  alkyl, C 2 -C 18  alkenyl; C 6 -C 10  aryl or C 6 -C 10  heteroaryl radical; —OR′; or —NR′R″; or R 1  and R 2  together form a 5- to 7-membered carbocyclic or heterocyclic ring; A is C 1 -C 5  alkyl; an unsubstituted or hydroxy-, C 1 -C 18  alkyl- or C 1 -C 18  alkoxy-substituted C 6 -C 10  aryl or heteroaryl radical; or a radical of formula (1a); R′ and R″ are each independently of the other hydrogen; unsubstituted or mono- or poly-hydroxy-, halo-, C 1 -C 18  alkyl-, C 1 -C 18  alkoxy-, amino- or quaternary ammonium group-substituted C 1 -C 18  alkyl, C 5 -C 7  cycloalkyl or phenyl; R 3  is hydrogen; or C 1 -C 6  alkyl; and n is 0 or 1. The compounds according to the invention are suitable especially as sun protective agents in cosmetic, pharmaceutical and veterinary medicine preparations.

[0001] The present invention relates to novel triazine derivatives, to aprocess for the preparation of such compounds and to the use of suchcompounds for cosmetic preparations.

[0002] The novel triazine derivatives correspond to the formula

[0003] wherein

[0004] R₁ is a C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₆-C₁₀aryl orC₆-C₁₀heteroaryl radical each unsubstituted or mono- or poly-substitutedby hydroxy, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, amino, C₁-C₅mono-alkylamino or bydi-C₁-C₅alkylamino; C₅-C₇cycloalkyl or C₅-C₇cycloalkenyl eachunsubstituted or substituted by C₁-C₅alkyl; —OR′; or —NR′R″;

[0005] R₂ is hydrogen; a C₁-C₁₈alkyl, C₂-C₁₈alkenyl; C₆-C₁₀aryl orC₆-C₁₀heteroaryl radical each unsubstituted or mono- or poly-substitutedby hydroxy, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, cyano, amino,

[0006] C₁-C₅monoalkylamino or by di-C₁-C₅alkylamino; —OR′; or —NR′R″; or

[0007] R₁ and R₂ together form a 5- to 7-membered carbocyclic orheterocyclic ring;

[0008] A is C₁-C₅alkyl; an unsubstituted or hydroxy-, C₁-C₁₈alkyl- orC₁-C₁₈alkoxy-substituted

[0009] C₆-C₁₀aryl or C₆-C₁₀heteroaryl radical; or a radical of formula(1a)

[0010] R′ and R″ are each independently of the other hydrogen;unsubstituted or mono- or poly-hydroxy-, halo-, C₁-C₁₈alkyl-,C₁-C₁₈alkoxy-, amino- or quaternary ammonium group-substitutedC₁-C₁₈alkyl, C₅-C₇cycloalkyl or phenyl;

[0011] R₃ is hydrogen; or C₁-C₆alkyl; and

[0012] n is 0 or 1.

[0013] C₁-C₁₈Alkyl denotes straight-chain or branched hydrocarbonradicals, for example methyl, ethyl, propyl, isopropyl, n-butyl,sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl,1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl,isoheptyl, 1,1,3,3-tetra-methylbutyl, 1-methylheptyl, 3-methylheptyl,n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl,nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, tridecyl, tetradecyl,pentadecyl or hexadecyl or octadecyl.

[0014] C₁-C₁₈Alkoxy denotes straight-chain or branched radicals, forexample methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, n-hexyloxy,1-methylhexyloxy, n-heptyloxy, isoheptyloxy, 1,1,3,3-tetramethyl-butoxy,1-methylheptyloxy, 3-methylheptyloxy, n-octyloxy, 2-ethylhexyloxy,1,1,3-tri-methylhexyloxy, 1,1,3,3-tetramethylpentyloxy, nonyloxy,decyloxy, undecyloxy, 1-methylundecyloxy, dodecyloxy, tridecyloxy,tetradecyloxy, pentadecyloxy, hexadecyloxy or octadecyloxy.

[0015] C₂-C₁₈Alkenyl is, for example, allyl, methallyl, isopropenyl,2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl,3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl,n-dodec-2-enyl or n-octadec-4-enyl.

[0016] C₆-C₁₈Aryl is, for example, phenyl or naphthyl.

[0017] A heterocyclic ring is a heteroaromatic system containing atleast one oxygen, sulfur and/or nitrogen hetero atom in the ringstructure. Preferred heteroaryl groups preferably contain from 2 to 15carbon atoms.

[0018] Examples of mono- or di-C₁-C₅alkylamino are methylamino,ethylamino, propylamino, n-butylamino, sec-butylamino, tert-butylamino,pentylamino, dimethylamino, diethylamino, dipropylamino, dibutylaminoand methyl-ethylamino.

[0019] Preference is given to triazine derivatives of formula (1)wherein

[0020] R₁ and R₂ are each independently of the other C₁-C₁₈alkyl orphenyl each unsubstituted or substituted by C₁-C₅alkyl, hydroxy or byC₁-C₅alkoxy; —OR′; or —NR′R″; or R₁ and R₂ together form a 5- to7-membered carbocyclic or heterocyclic ring.

[0021] More especially preferred are compounds of formula (1) wherein

[0022] R₁ is C₁-C₅alkyl; C₁-C₅alkoxy; or unsubstituted or C₁-C₅alkyl-,hydroxy- or C₁-C₅alkoxy-substituted phenyl.

[0023] Also preferred are compounds of formula (1) wherein

[0024] R₂ is hydrogen; C₁-C₅alkyl; C₁-C₅alkoxy; unsubstituted orhydroxy-, C₁-C₅alkyl- or C₁-C₅-alkoxy-substituted phenyl; and

[0025] n is 1.

[0026] Preference is also given to compounds of formula (1) wherein

[0027] R₁ and R₂ together are a —(CH₂)₂₋₅— radical that is not furthersubstituted or is substituted by one or more C₁-C₅alkyl and isuninterrupted or interrupted by one or two —O— and/or —NH— groups and/or

[0028] Very special preference is given to compounds of formula (1)wherein

[0029] R₁ and R together are a

[0030] radical;

[0031] R₅ is hydrogen; or C₁-C₅alkyl.

[0032] A in formula (1) is especially amino; phenyl; orC₁-C₅alkoxyphenyl.

[0033] R₃ in formula (1) is especially hydrogen.

[0034] Special preference is given to compounds of formula (1) whereinR₁ and R₂ are C₁-C₅alkyl.

[0035] Examples of compounds according to the invention are listed inTable 1 below: TABLE 1

Compound of formula R₁ R₂ (2)

(3)

(4)

(5)

(6)

(7)

(8)

(9)

(10)

(11) *—O—CH₃

(12)

H (13)

(14)

(15)

(16)

H (17) *—CH₃

(18) *—O—C₂H₅

(19)

(20)

**—CN (21)

(22)

(23)

(24)

(25)

(26)

H (27)

H (28)

H (29)

(30)

(31) *—CH₃

[0036] Especially preferred are compounds of formulae

[0037] The triazine derivatives of formula (1) according to theinvention are prepared in a manner known per se by reacting adiaminotriazine compound of formula

[0038] with a compound of formula

[0039] wherein

[0040] R₄ is C₁-C₅alkyl and R₁, R₂, R₃, A and n are as defined forformula (1), to form a compound of formula (1).

[0041] The reaction is carried out in the presence of an acid, with orwithout the addition of one or more solvents at a reaction temperatureof from 0 to 200° C.

[0042] Generally from 0.8 to 2.0 mol of the compound of formula (1b) andfrom 0.8 to 2.0 mol of a compound of formula (1c) are used per freeamino group of compound (1a).

[0043] The reaction is preferably carried out in DMSO,N-methylpyrrolidone, DMF or DMA. It is also possible, however, to useprotic solvents, such as ethanol, methanol, isobutanol or isopropanol.The reaction can also be carried out in an aliphatic or aromaticsolvent, such as hexane, toluene or xylene. It is also possible to useethers, such as diethyl ether and tetrahydrofuran, or halogenatedsolvents, such as chloroform or dichloromethane.

[0044] The reaction is preferably carried out as a one-pot reaction. Theindividual reactants may, however, be added in any desired order. Forexample, the catalyst may be present from the beginning or may beintroduced only later. It is also possible first to start the reactionbetween (1b) and (1c) in the presence of the catalyst and only later toadd the triazine compound of formula (1a). It is equally possible firstto react the compound of formula (1a) with the compound of formula (1b)in the presence of a catalyst and to add (1c) later. The reaction can becarried out at a temperature of from 0 to 200° C., preferably at from 20to 100° C. and especially from 50 to 80° C.

[0045] The reaction times are dependent upon the reaction temperature.Within the preferred temperature range, the reactions are generallycompleted within from 1 to 6 hours. At low temperatures, the reactiontime increases considerably and may be 48 hours or more.

[0046] As catalysts there are used organic and inorganic Brönstedt orLewis acids or mixtures thereof. Examples of typical acids arephosphoric acid, trifluoroacetic acid, oxalic acid, methanesulfonicacid, toluenesulfonic acid, phenylsulfonic acid andtrifluoromethanesulfonic acid. Also effective are acid anhydrides, forexample trifluoromethanesulfonic anhydride, methanesulfonic anhydrideand acetic anhydride. Preference is given, however, to the use of

[0047] Lewis acids, such as phosphorus oxychloride, copper chlorides,zinc chloride, lanthanum chloride, chromium chlorides, iron chlorides,aluminium chloride, titanium chlorides, germanium chloride, and hydratesthereof. It is also possible to use acidic ion exchangers.

[0048] The product is isolated according to conventional techniques,such as filtration, centrifugation, phase separation and liquidextraction. The products are purified, inter alia, by recrystallisationfrom a solvent or from a solvent mixture, preference being given tosolvents or solvent mixtures containing alcohols. Purification can alsobe carried out by chromatographic methods and by distillation.

[0049] The compounds of formula (1) according to the invention aresuitable especially as UV filters, that is to say to protect organicmaterials that are sensitive to ultraviolet light, especially human andanimal skin and hair, against the damaging effect of UV radiation. Thecompounds are accordingly suitable as light-protective agents incosmetic, pharmaceutical and veterinary medicine preparations. Thecompounds can be used either in the dissolved state or in the micronisedstate.

[0050] The invention accordingly relates also to a cosmetic preparationcomprising at least one compound of formula (1), and to cosmeticallytolerable carriers or adjuvants.

[0051] In addition to the UV absorber according to the invention, thecosmetic preparation may also comprise one or more further UV protectivesubstances of the following substance classes:

[0052] 1. p-aminobenzoic acid derivatives, for example4-dimethylaminobenzoic acid 2-ethylhexyl ester;

[0053] 2. salicylic acid derivatives, for example salicylic acid2-ethylhexyl ester;

[0054] 3. benzophenone derivatives, for example2-hydroxy-4-methoxybenzophenone and its 5-sulfonic acid derivative;

[0055] 4. dibenzoylmethane derivatives, for example1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-propane-1,3-dione;

[0056] 5. diphenylacrylates, for example 2-ethylhexyl2-cyano-3,3-diphenylacrylate, and 3-(benzofuranyl) 2-cyanoacrylate;

[0057] 6. 3-imidazol-4-ylacrylic acid and esters;

[0058] 7. benzofuran derivatives, especially 2-(p-aminophenyl)benzofuranderivatives, described in EP-A-582 189, U.S. Pat. No. 5,338,539, U.S.Pat. No. 5,518,713 and EP-A-613 893;

[0059] 8. polymeric UV absorbers, for example the benzylidene malonatederivatives described in EP-A-709 080;

[0060] 9. cinnamic acid derivatives, for example the 4-methoxycinnamicacid 2-ethylhexyl ester and isoamyl ester or cinnamic acid derivativesdisclosed in U.S. Pat. No. 5,601,811 and WO 97/00851;

[0061] 10. camphor derivatives, for example3-(4′-methyl)benzylidene-bornan-2-one, 3-benzylidenebornan-2-one,N-[2(and 4)-2-oxyborn-3-ylidene-methyl)-benzyl]acrylamide polymer,3-(4′-trimethylammonium)-benzylidene-bornan-2-one methyl sulfate,3,3′-(1,4-phenylenedimethine)-bis(7,7-dimethyl-2-oxo-bicyclo[2.2.1]heptane-1-methanesulfonicacid) and salts, 3-(4′-sulfo)benzylidene-bornan-2-one and salts;camphorbenzalkonium methosulfate;

[0062] 11. hydroxyphenyltriazine compounds, for example2-(4′-methoxyphenyl)-4,6-bis(2′-hydroxy-4′-n-octyloxyphenyl)-1,3,5-triazine;2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-[4-(2-methoxyethyl-carboxyl)-phenylamino]-1,3,5-triazine;2,4-bis{[4-(tris(trimethylsilyloxy-silylpropyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(2″-methylpropenyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(1′,1′,1′,3′,5′,5′,5′-heptamethyltrisilyl-2″-methyl-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl[-6-}4-ethyicarboxy)-phenylamino]-1,3,5-triazine;

[0063] 12. benzotriazole compounds, for example2,2′-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol

[0064] 13. trianilino-s-triazine derivatives, for example2,4,6-trianiline-(p-carbo-2′-ethyl-1′-oxy)-1,3,5-triazine and the UVabsorbers disclosed in U.S. Pat. No. 5,332,568, EP-A-517 104, EP-A-507691, WO 93/17002 and EP-A-570 838;

[0065] 14. 2-phenylbenzimidazole-5-sulfonic acid and salts thereof;

[0066] 15. menthyl o-aminobenzoate;

[0067] 16. TiO₂ (variously encapsulated), ZnO and mica.

[0068] The UV absorbers described in “Sunscreens”, Eds. N. J. Lowe, N.A. Shaath, Marcel Dekker, Inc., New York and Basle or in Cosmetics &Toiletries (107), 50ff (1992) also can be used as additional UVprotective substances.

[0069] Special preference is given to the light-protective agentsindicated in the following Table: INCI Chemical Name CAS No.3-BENZYLIDENE CAMPHOR 1,7,7-trimethyl-3-(phenylmethylene)- 15087-24-8bicyclo[2.2.1]heptan-2-one 4-METHYLBENZYLIDENE(+/−)-1,7,7-trimethyl-3-[(4-methylphenyl)- 36861-47-9 CAMPHORmethylene]bicyclo[2.2.1]heptan-2-one BENZOPHENONE-10(2-hydroxy-4-methoxyphenyl)-(4-methylphenyl) 1641-17-4 methanoneBENZOPHENONE-1 2,4-dihydroxybenzophenone 131-56-6 BENZOPHENONE-22,2′,4,4′-tetrahydroxybenzophenone 131-55-5 BENZOPHENONE-32-hydroxy-4-methoxybenzophenone; 131-57-7 BENZOPHENONE-42-hydroxy-4-methoxybenzophenone-5- 4065-45-6 sulfonic acidBENZOPHENONE-6 2,2′-dihydroxy-4,4′-dimethoxybenzophenone 131-54-4BENZOPHENONE-8 2,2′-dihydroxy-4-methoxybenzophenone 131-53-3 BENZYLIDENECAMPHOR alpha-(2-oxoborn-3-ylidene)-toluene-4-sulfonic 56039-58-8SULFONIC ACID acid and its salts BUTYL METHOXY-1-[4-(1,1-dimethylethyl)phenyl]-3-(4- 70356-09-1 DIBENZOYLMETHANEmethoxyphenyl)propane-1,3-dione CAMPHOR BENZALKONIUM methylN,N,N-trimethyl-4-[(4,7,7-trimethyl-3- 52793-97-2 METHOSULFATEoxobicyclo[2,2,1]hept-2-ylidene)- methyl]anilinium sulfate CINOXATE2-ethoxyethyl p-methoxycinnamate 104-28-9 DEA-METHOXYCINNAMATEdiethanolamine salt of p-methoxy- 56265-46-4 hydrocinnamate DIISOPROPYLMETHYL 2-propenoic acid, 3-[2,4-bis(1- 32580-71-5 ClNNAMATEmethylethyl)phenyl]-, methyl ester DIPROPYLENE GLYCOL dipropylene glycolsalicylate 7491-14-7 SALICYLATE ETHYL DIHYDROXYPROPYL ethyl4-bis(2-hydroxypropyl)-amino-benzoate 58882-17-0 PABA ETHYLDIISOPROPYLCINNAMATE ethyl 3-[2,4-bis(1-methylethyl)phenyl]- 32580-72-6acrylate ETHYL METHOXYCINNAMATE ethyl p-methoxycinnamate 1929-30-2GLYCERYL OCTANOATE DIMETHOXYCINNAMATE GLYCERYL PABA glyceryl1-(4-aminobenzoate) 136-44-7 HOMOSALATE3,3,5-trimethylcyclohexyl-2-hydroxy-benzoate 118-56-9 ISOAMYLp-METHOXYCINNAMATE isopentyl p-methoxycinnamate 71617-10-2 ISOPROPYLDIBENZOYLMETHANE 1-[4-(1-methylethyl)phenyl]-3-phenyl- 63250-25-9propane-1,3-dione ISOPROPYL METHOXYCINNAMATE isopropylp-methoxycinnamate 5466-76-2 LAWSONE 2-hydroxy-1,4-naphthoquinone83-72-7 MENTHYL ANTHRANILATE menthyl o-aminobenzoate 134-09-8 MENTHYLSALICYLATE menthyl salicylate 89-46-3 OCTOCRYLENE 2-ethylhexyl2-cyano-3,3-diphenyl acrylate 6197-30-4 ETHYLHEXYL DIMETHYL PABA2-ethylhexyl 4-(dimethylamino)benzoate 21245-02-3 ETHYLHEXYLMETHOXYCINNAMATE 2-ethylhexyl 4-methoxycinnamate 5466-77-3 ETHYLHEXYLSALICYLATE 2-ethylhexyl salicylate 118-60-5 ETHYLHEXYL TRIAZONE benzoicacid, 4,4′,4″-(1,3,5-triazine-2,4,6- 88122-99-0 triyltriimino)tris-,tris(2-ethylhexyl) ester;2,4,6-trianilino-(p-carbo-2′-ethylhexyl-1′-oxy)- 1,3,5-triazine PABA4-aminobenzoic acid 150-13-0 PEG-25 PABA benzoic acid, 4-amino-, ethylester, 113010-52-9 polymer with oxirane PENTYL DIMETHYL PABA amyldimethyl PABA 14779-78-3 PHENYLBENZIMIDAZOLE2-phenyl-1H-benzimidazole-5-sulfonic 27503-81-7 SULFONIC ACID acidPOLYACRYLAMIDOMETHYL 113783-61-2 BENZYLIDENE CAMPHOR TEA-SALICYLATEtriethanolamine salicylate 2174-16-5 TEREPHTHALYLIDENE DICAMPHOR3,3′-(1,4-phenylenedimethylene)bis[7,7- 90457-82-2 SULFONIC ACIDdimethyl-2-oxo-bicyclo[2.2.1]heptane-1- methanesulfonic acid] TITANIUMDIOXIDE titanium dioxide 13463-67-7 DIGALLOYL TRIOLEATE digalloyltrioleate 17048-39-4 ZINC OXIDE zinc oxide 1314-13-2 Methylenebis-benzotriazolyl 2,2′-methylene-bis[6-(2H-benzotriazol-2-yl)-4-103597-45-1 tetramethylbutylphenol (1,1,3,3-tetramethylbutyl)-phenol]Bis-ethylhexyloxyphenol 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]-187393-00-6 methoxyphenyltriazinephenyl}-6-(4-methoxyphenyl)-(1,3,5)-triazine BISIMIDAZYLATE1H-benzimidazole-4,6-disulfonic acid, 180898-37-72,2′-(1,4-phenylene)bis-, disodium salt DIETHYLHEXYL BUTAMIDO benzoicacid, 4,4′-[[6-[[4-[[(1,1-dimethyl- 154702-15-5 TRIAZONEethyl)amino]carbonyl]phenyl]amino]-1,3,5-triazine-2,4-diyl]diimino]bis-, bis(2-ethyl- hexyl) ester DROMETRIZOLETRISILOXANE phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6- 155633-54-8[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]- BENZYLIDENE MALONATEalpha-(trimethylsilyl)-omega-(trimethyl-silyloxy) 207574-74-1POLYSILOXANE poly[oxy(dimethyl)silylene]-co-[oxy-(methyl)(2-{p-[2,2-bis(ethoxycarbonyl)vinyl]-phenoxy}-1-methyleneethyl)silylene]-co-[oxy-(methyl)(2-{p-[2,2-bis(ethoxycarbonyl)vinyl]-phenoxy}prop-1-enyl)silylene]2-(4-diethylamino-2-hydroxybenzoyl)-benzoic 302776-68-7 hexyl ester

[0070] Each of the above-mentioned light-protective agents, especiallythe light-protective agents in Table 1 indicated as being preferred, canbe used in admixture with the UV absorbers according to the invention.It will be understood in that connection that, in addition to the UVabsorbers according to the invention, it is also possible for more thanone of the additional light-protective agents to be used, for example,two, three, four, five or six further light-protective agents.

[0071] Preference is given to the use of mixing ratios of UV absorbersaccording to the invention/further light-protective agents of from 1:99to 99:1, especially from 1:95 to 95:1 and preferably from 10:90 to90:10, based on weight. Of special interest are mixing ratios of from20:80 to 80:20, especially from 40:60 to 60:40 and preferably ofapproximately 50:50. Such mixtures can be used, inter alia, to improvesolubility or increase UV absorption.

[0072] Appropriate mixtures can be used especially advantageously in thecosmetic preparations described below.

[0073] The cosmetic preparations are suitable especially as UV filters,that is to say for the protection of organic materials that aresensitive to ultraviolet light, especially skin and hair, against thedamaging effect of UV radiation.

[0074] The UV absorbers can be used either in the dissolved state or inthe micronised state.

[0075] Any known process suitable for the preparation of microparticlescan be used for the preparation of the micronised UV absorbers, forexample:

[0076] wet-grinding with a hard grinding medium, for example zirconiumsilicate and a protective surfactant or a protective polymer in water orin a suitable organic solvent;

[0077] spray-drying from a suitable solvent, for example aqueoussuspensions or suspensions containing organic solvents, or truesolutions in water, ethanol, dichloroethane, toluene,N-methylpyrrolidone inter alia;

[0078] by the expansion according to the RESS process (Rapid Expansionof Supercritical Solutions) of supercritical fluids (e.g. CO₂) in whichthe UV filter or filters is/are dissolved or the expansion of fluidcarbon dioxide together with a solution of one or more UV filters in asuitable organic solvent;

[0079] by reprecipitation from suitable solvents, includingsupercritical fluids (GASR process=Gas Anti-SolventRecrystallisation/PCA process=Precipitation with CompressedAntisolvents).

[0080] As grinding apparatus for the preparation of the micronisedorganic UV absorbers there may be used, for example, a let mill, ballmill, vibratory mill or hammer mill, preferably a high-speed mixingmill. The grinding is preferably carried out with a grinding aid, forexample an alkylated vinylpyrrolidone polymer, a vinylpyrrolidone/vinylacetate copolymer, an acyl glutamate, an alkyl polyglucoside,ceteareth-25 or a phospholipid.

[0081] The micronised UV absorbers so obtained usually have an averageparticle size that is from 0.02 to 2, preferably from 0.05 to 1.5, andmore especially from 0.1 to 1.0, nm.

[0082] The UV absorbers can also be used dry in powder form. For thatpurpose the UV absorbers are subjected to known grinding methods, suchas vacuum atomization, countercurrent spray-drying etc. Such powdershave a particle size of from 0.1 nm to 2 μm. To avoid the occurrence ofagglomeration, the UV absorbers can be coated with a surface-activecompound prior to the pulverisation process, for example with ananionic, non-ionic or amphoteric surfactant, e.g. a phospholipid or aknown polymer, such as PVP, an acrylate etc.

[0083] The cosmetic preparations contain, for example, from 0.1 to 30%by weight, preferably from 0.1 to 15% by weight and especially from 0.5to 10% by weight, based on the total weight of the composition, of oneor more UV absorbers and at least one cosmetically tolerable adjuvant.

[0084] The cosmetic preparations can be prepared by physically mixingthe UV absorber(s) with the adjuvant using customary methods, forexample by simply stirring together the individual components,especially by making use of the dissolution properties of already knowncosmetic UV absorbers, for example OMC, salicylic acid isooctyl ester,inter alia. The UV absorber can be used, for example, without furthertreatment, or in the micronised state, or in the form of a powder.

[0085] The cosmetic preparations may be, for example, creams, gels,lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fatcompositions, stick preparations, powders or ointments.

[0086] As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O andW/O/W emulsions or microemulsions) the preparations contain, forexample,

[0087] from 0.1 to 30% by weight, preferably from 0.1 to 15% by weightand especially from 0.5 to 10% by weight, based on the total weight ofthe composition, of one or more UV absorbers,

[0088] from 1 to 60% by weight, especially from 5 to 50% by weight andpreferably from 10 to 35% by weight, based on the total weight of thecomposition, of at least one oil component,

[0089] from 0 to 30% by weight, especially from 1 to 30% by weight andpreferably from 4 to 20 % by weight, based on the total weight of thecomposition, of at least one emulsifier,

[0090] from 10 to 90% by weight, especially from 30 to 90% by weight,based on the total weight of the composition, of water, and

[0091] from 0 to 88.9% by weight, especially from 1 to 50% by weight, offurther cosmetically tolerable adjuvants.

[0092] As oil components of oil-containing compositions (e.g. oils, W/O,OW, O/W/0 and W/O/W emulsions or microemulsions) there come intoconsideration, for example, Guerbet alcohols based on fatty alcoholshaving from 6 to 18, preferably from 8 to 10, carbon atoms, esters oflinear C₆-C₂₄ fatty acids with linear C₃-C₂₄ alcohols, esters ofbranched C₆-C₁₃carboxylic acids with linear C₆-C₂₄ fatty alcohols,esters of linear C₆-C₂₄ fatty acids with branched alcohols, especially2-ethylhexanol, esters of hydroxycarboxylic acids with linear orbranched C₆-C₂₂ fatty alcohols, especially dioctyl malates, esters oflinear and/or branched fatty acids with polyhydric alcohols (for examplepropylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols,triglycerides based on C₆-C₁₀ fatty acids, liquidmono-/di-/tri-glyceride mixtures based on C₆-C₁₈ fatty acids, esters ofC₆-C₂₄ fatty alcohols and/or Guerbet alcohols with aromatic carboxylicacids, especially benzoic acid, esters of C₂-C₁₂dicarboxylic acids withlinear or branched alcohols having from 1 to 22 carbon atoms or polyolshaving from 2 to 10 carbon atoms and from 2 to 6 hydroxy groups,vegetable oils (such as sunflower oil, olive oil, soybean oil, rapeseedoil, almond oil, jojoba oil, orange oil, wheatgerm oil, peach kernel oiland the liquid components of coconut oil), branched primary alcohols,substituted cyclohexanes, linear and branched C₆-C₂₂ fatty alcoholcarbonates, Guerbet carbonates, esters of benzoic acid with linearand/or branched C₆-C₂₂alcohols (e.g. Finsolv® TN), linear or branched,symmetric or asymmetric dialkyl ethers having a total of from 12 to 36carbon atoms, especially from 12 to 24 carbon atoms, for exampledi-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n-undecylether, di-n-dodecyl ether, n-hexyl n-octyl ether, n-octyl n-decyl ether,n-decyl n-undecyl ether, n-undecyl n-dodecyl ether, n-hexyl n-undecylether, di-tert-butyl ether, diisopentyl ether, di-3-ethyidecyl ether,tert-butyl n-octyl ether, isopentyl n-octyl ether and 2-methylpentyl-n-octyl ether; ring-opening products of epoxidised fatty acidesters with polyols, silicone oils and/or aliphatic or naphthenichydrocarbons. Also of importance are monoesters of fatty acids withalcohols having from 3 to 24 carbon atoms. That group of substancescomprises the esterification products of fatty acids having from 8 to 24carbon atoms, for example caproic acid, caprylic acid, 2-ethylhexanoicacid, capric acid, lauric acid, isotridecanoic acid, myristic acid,palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleicacid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid,elaeostearic acid, arachidic acid, gadoleic acid, behenic acid anderucic acid and technical-grade mixtures thereof (obtained, for example,in the pressure removal of natural fats and oils, in the reduction ofaldehydes from Roelen's oxosynthesis or in the dimerisation ofunsaturated fatty acids) with alcohols, for example, isopropyl alcohol,caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol,lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol,palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol,elaidyl alcohol, petroselinyl alcohol, linoyl alcohol, linolenylalcohol, elaeostearyl alcohol, arachidyl alcohol, gadoleyl alcohol,behenyl alcohol, erucyl alcohol and brassidyl alcohol andtechnical-grade mixtures thereof (obtained, for example, in thehigh-pressure hydrogenation of technical-grade methyl esters based onfats and oils or aldehydes from Roelen's oxosynthesis and as monomerfractions in the dimerisation of unsaturated fatty alcohols). Of specialimportance are isopropyl myristate, isononanoic acid C₁₆-C₁₈alkylesters, stearic acid 2-ethylhexyl ester, cetyl oleate, glyceroltricaprylate, coconut fatty alcohol caprinate/caprylate and n-butylstearate. Further oil components that can be used are dicarboxylic acidesters, such as di-n-butyl adipate, di(2-ethylhexyl) adipate,di(2-ethylhexyl) succinate and diisotridecyl acetate, and also diolesters, such as ethylene glycol dioleate, ethylene glycoldiisotridecanoate, propylene glycol di(2-ethylhexanoate), propyleneglycol diisostearate, propylene glycol dipelargonate, butanedioldiisostearate and neopentyl glycol dicaprylate. Preferred mono- orpoly-ols are ethanol, isopropanol, propylene glycol, hexylene glycol,glycerol and sorbitol. It is also possible to use di- and/or tri-valentmetal salts (alkaline earth metal, Al³⁺ inter alia) of one or morealkylcarboxylic acids.

[0093] The oil components can be used in an amount of, for example, from1 to 60% by weight, especially from 5 to 50% by weight and preferablyfrom 10 to 35% by weight, based on the total weight of the composition.

[0094] Any conventionally usable emulsifier can be used for thecompositions.

[0095] As emulsifiers there come into consideration, for example,non-ionic surfactants from the following groups:

[0096] addition products of from 2 to 30 mol of ethylene oxide and/orfrom 0 to 5 mol of propylene oxide with linear fatty alcohols havingfrom 8 to 22 carbon atoms, with fatty acids having from 12 to 22 carbonatoms and with alkylphenols having from 8 to 15 carbon atoms in thealkyl group, for example ceteareth-20 or ceteareth-12;

[0097] C₁₂-C₂₂ fatty acid mono- and di-esters of addition products offrom 1 to 30 mol of ethylene oxide with polyols having from 3 to 6carbon atoms, especially with glycerol;

[0098] glycerol mono- and di-esters and sorbitan mono- and di-esters ofsaturated and unsaturated fatty acids having from 6 to 22 carbon atomsand ethylene oxide addition products thereof, for example glycerylstearates, glyceryl isostearates, glyceryl oleates, sorbitan oleates orsorbitan sesquioleates;

[0099] C₈-C₂₂alkyl-mono- and -oligo-glycosides and ethoxylated analoguesthereof, degrees of oligomerisation of from 1.1 to 5, especially from1.2 to 1.4, being preferred, and glucose being preferred as the sugarcomponent;

[0100] addition products of from 2 to 60 mol. especially from 15 to 60mol, of ethylene oxide with castor oil and/or hardened castor oil;

[0101] polyol esters and especially polyglycerol esters, for examplediisostearoyl polyglyceryl-3-diisostearates,polyglyceryl-3-diisostearates, triglyceryl diisostearates,polyglyceryl-2-sesquiisostearates or polyglyceryl dimerates. Mixtures ofcompounds from a plurality of those substance classes are also suitable;

[0102] partial esters based on linear, branched, unsaturated orsaturated C₆-C₂₂ fatty acids, ricinoleic acid and also 12-hydroxystearicacid and on glycerol, polyglycerol, pentaerythritol, dipentaerythritol,sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside,butyl glucoside, lauryl glucoside) and also polyglucosides (e.g.cellulose), for example polyglyceryl-2-dihydroxystearates orpolyglyceryl-2-diricinoleates;

[0103] mono-, di- and tri-alkylphosphates and also mono-, di- and/ortri-PEG-alkylphosphates and salts thereof;

[0104] wool wax alcohols;

[0105] one or more ethoxylated esters of natural derivatives, forexample polyethoxylated esters of hydrogenated castor oil;

[0106] silicone oil emulsifiers, for example silicone polyol;

[0107] polysiloxane/polyalkyl/polyether copolymers and correspondingderivatives, for example cetyl dimethicone copolyol;

[0108] mixed esters of pentaerythritol, fatty acids, citric acid andfatty alcohol (see DE-A-1 165 574) and/or mixed esters of fatty acidshaving from 6 to 22 carbon atoms, methylglucose and polyols, preferablyglycerol or polyglycerol, for example polyglyceryl-3-glucosedistearates, polyglyceryl-3-glucose dioleates, methyl glucose dioleatesor dicocoyl pentaerythryl distearyl citrates and also

[0109] polyalkylene glycols.

[0110] The addition products of ethylene oxide and/or of propylene oxidewith fatty alcohols, fatty acids, alkylphenols, glycerol mono- anddi-esters and also sorbitan mono- and di-esters of fatty acids, or withcastor oil, are known, commercially available products. They are usuallyhomologue mixtures, the average degree of alkoxylation of whichcorresponds to the ratio of the amounts of ethylene oxide and/orpropylene oxide and substrate with which the addition reaction iscarried out. C₁₂-C₁₈ fatty acid mono- and di-esters of addition productsof ethylene oxide with glycerol are known, for example, from DE-A-2 024051 as fat-restoring substances for cosmetic preparations.

[0111] C₁-C₁₈Alkyl-mono- and -oligo-glycosides, their preparation andtheir use are known from the prior art. They are prepared especially byreacting glucose or oligosaccharides with primary alcohols having from 8to 18 carbon atoms. Suitable glycoside radicals include mono-glycosidesin which a cyclic sugar radical is glycosidically bonded to the fattyalcohol and also oligomeric glycosides having a degree ofoligomerisation of up to preferably about 8. The degree ofoligomerisation is a statistical average value based on a homologuedistribution customary for such technical-grade products.

[0112] It is also possible to use zwitterionic surfactants asemulsifiers. The term “zwitterionic surfactants” denotes especiallysurface-active compounds that carry at least one quaternary ammoniumgroup and at least one carboxylate and/or sulfonate group in themolecule. Zwitterionic surfactants that are especially suitable are theso-called betaines, such as N-alkyl-N,N-dimethylammonium glycinates, forexample cocoalkyldimethylammonium glycinate,N-acylaminopropyl-N,N-dimethylammonium glycinates, for examplecocoacylaminopropyldimethylammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from 8 to18 carbon atoms in the alkyl or acyl group and alsococoacylaminoethylhydroxyethylcarboxymethylglycinate. Special preferenceis given to the fatty acid amide derivative known by the CTFA namecocamidopropyl betaine. Likewise suitable as emulsifiers are ampholyticsurfactants. Ampholytic surfactants are to be understood as meaningespecially those which, in addition to containing a C₈-C₁₈-alkyl or-acyl group, contain at least one free amino group and at least one—COOH or —SO₃H group in the molecule and are capable of forming internalsalts. Examples of suitable ampholytic surfactants includeN-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids,N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines,N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoaceticacids, each having approximately from 8 to 18 carbon atoms in the alkylgroup. Ampholytic surfactants to which special preference is given areN-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate andC₁₂-C₁₈-acylsarcosine. In addition to the ampholytic emulsifiers therealso come into consideration quaternary emulsifiers, special preferencebeing given to those of the esterquat type, preferablymethyl-quaternised di-fatty acid triethanolamine ester salts.

[0113] Non-ionic emulsifiers are preferred. Of the non-ionic emulsifiersmentioned, special preference is given to ethoxylated fatty alcoholshaving from 8 to 22 carbon atoms and from 4 to 30 EO units.

[0114] The emulsifiers may be used in an amount of, for example, from 1to 30% by weight, especially from 4 to 20% by weight and preferably from5 to 10% by weight, based on the total weight of the composition. It is,however, also possible in principle to dispense with the use ofemulsifiers.

[0115] The preparations according to the invention, for example creams,gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions,wax/fat compositions, stick preparations, powders or ointments, may inaddition contain, as further adjuvants and additives, mild surfactants,super-fatting agents, pearlescent waxes, consistency regulators,thickeners, polymers, silicone compounds, fats, waxes, stabilisers,biogenic active ingredients, deodorising active ingredients,anti-dandruff agents, film formers, swelling agents, further UVlight-protective factors, antioxidants, hydrotropic agents,preservatives, insect repellents, self-tanning agents, solubilisers,perfume oils, colourants, bacteria-inhibiting agents and the like.

[0116] Substances suitable for use as super-fatting agents are, forexample, lanolin and lecithin and also polyethoxylated or acrylatedlanolin and lecithin derivatives, polyol fatty acid esters,monoglycerides and fatty acid alkanolamides, the latter simultaneouslyacting as foam stabilisers.

[0117] Examples of suitable mild surfactants, that is to say surfactantsespecially well tolerated by the skin, include fatty alcohol polyglycolether sulfates, monoglyceride sulfates, mono- and/or di-alkylsulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fattyacid taurides, fatty acid glutamates, α-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides,alkylamidobetaines and/or protein fatty acid condensation products, thelatter preferably being based on wheat proteins.

[0118] As pearlescent waxes there come into consideration, for example:alkylene glycol esters, especially ethylene glycol distearate; fattyacid alkanolamides, especially coco fatty acid di-ethanolamide; partialglycerides, especially stearic acid monoglyceride; esters of polyvalent,unsubstituted or hydroxy-substituted carboxylic acids with fattyalcohols having from 6 to 22 carbon atoms, especially long-chainedesters of tartaric acid; fatty substances, for example fatty alcohols,fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, whichin total have at least 24 carbon atoms, especially laurone and distearylether; fatty acids, such as stearic acid, hydroxystearic acid or behenicacid, ring-opening products of olefin epoxides having from 12 to 22carbon atoms with fatty alcohols having from 12 to 22 carbon atomsand/or polyols having from 2 to 15 carbon atoms and from 2 to 10 hydroxygroups, and mixtures thereof.

[0119] As consistency regulators there come into considerationespecially fatty alcohols or hydroxy fatty alcohols having from 12 to 22carbon atoms and preferably from 16 to 18 carbon atoms, and in additionpartial glycerides, fatty acids and hydroxy fatty acids. Preference isgiven to a combination of such substances with alkyl-oligoglucosidesand/or fatty acid N-methylglucamides of identical chain length and/orpolyglycerol poly-12-hydroxystearates. Suitable thickeners include, forexample, Aerosil types (hydrophilic silicic acids), polysaccharides,especially xanthan gum, guar-guar, agar-agar, alginates and Tyloses,carboxymethyl cellulose and hydroxymethyl cellulose, also relativelyhigh molecular weight polyethylene glycol mono- and di-esters of fattyacids, polyacrylates (e.g. Carbopol® from Goodrich or Synthalen® fromSigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone,surfactants, for example ethoxylated fatty acid glycerides, esters offatty acids with polyols, for example pentaerythritol ortrimethylolpropane, fatty alcohol ethoxylates with restricted homologuedistribution and alkyl-oligoglucosides as well as electrolytes, such assodium chloride or ammonium chloride.

[0120] Suitable cationic polymers are, for example, cationic cellulosederivatives, for example a quaternised hydroxymethyl celluloseobtainable under the name Polymer JR 400® from Amerchol, cationicstarch, copolymers of diallylammonium salts and acrylamides, quaternisedvinylpyrrolidone/vinyl imidazole polymers, for example Luviquate®(BASF), condensation products of polyglycols and amines, quaternisedcollagen polypeptides, for example lauryldimonium hydroxypropylhydrolyzed collagen (Lamequat®L/Grünau), quaternised wheat polypeptides,polyethyleneimine, cationic silicone polymers, for exampleamidomethicones, copolymers of adipic acid anddimethylaminohydroxypropyldiethylenetriamine (Cartaretin®/Sandoz),copolymers of acrylic acid with dimethyidiallylammonium chloride(Merquate® 550/Chemviron), polyaminopolyamides, as described, forexample, in FR-A-2 252 840, and the crosslinked water-soluble polymersthereof, cationic chitin derivatives, for example of quaternisedchitosan, optionally distributed as microcrystals; condensation productsof dihaloalkyls, for example dibromobutane, with bisdialkylamines, forexample bisdimethylamino-1,3-propane, cationic guar gum, for exampleJaguar® C-17, Jaguar® C-16 from Celanese, quaternised ammonium saltpolymers, for example Mirapol® A-15, Mirapolo® AD-1, Mirapol® AZ-1 fromMiranol.

[0121] As anionic, zwitterionic, amphoteric and non-ionic polymers therecome into consideration, for example, vinyl acetate/crotonic acidcopolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinylacetate/butyl maleate/isobornyl acrylate copolymers, methyl vinylether/maleic anhydride copolymers and esters thereof, uncrosslinkedpolyacrylic acids and polyacrylic acids crosslinked with polyols,acrylamidopropyltrimethylammonium chloride/acrylate copolymers, octylacrylamide/methyl methacrylate/tert-butylaminoethylmethacrylate/2-hydroxypropyl methacrylate copolymers,polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers,vinylpyrrolidone/dimethylaminoethyl methacrylate/vinyl caprolactamterpolymers and also optionally derivatised cellulose ethers andsilicones.

[0122] Suitable silicone compounds are, for example,dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones, andalso amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-,glycoside- and/or alkyl-modified silicone compounds, which at roomtemperature may be in either liquid or resinous form. Also suitable aresimethicones, which are mixtures of dimethicones having an average chainlength of from 200 to 300 dimethylsiloxane units with hydrogenatedsilicates. A detailed survey by Todd et al. of suitable volatilesilicones may in addition be found in Cosm. Toil. 91, 27 (1976).

[0123] Typical examples of fats are glycerides, and as waxes there comeinto consideration, inter alia, beeswax, carnauba wax, candelilla wax,montan wax, paraffin wax, hydrogenated castor oils and fatty acid estersor microwaxes solid at room temperature optionally in combination withhydrophilic waxes, e.g. cetylstearyl alcohol or partial glycerides.Metal salts of fatty acids, for example magnesium, aluminium and/or zincstearate or ricinoleate, may be used as stabilisers.

[0124] Biogenic active ingredients are to be understood as meaning, forexample, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbicacid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol,panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essentialoils, plant extracts and vitamin complexes.

[0125] As deodorising active ingredients there come into consideration,for example, antiperspirants, for example aluminium chlorohydrates (seeJ. Soc. Cosm. Chem. 24, 281 (1973)). Under the trade mark Locron® ofHoechst AG, Frankfurt (FRG), there is available commercially, forexample, an aluminium chlorohydrate corresponding to formulaAl₂(OH)₅Cl×2.5 H₂O, the use of which is especially preferred (see J.Pharm. Pharmacol. 26, 531 (1975)). Besides the chlorohydrates, it isalso possible to use aluminium hydroxy-acetates and acidicaluminium/zirconium salts. Esterase inhibitors may be added as furtherdeodorising active ingredients. Such inhibitors are preferably trialkylcitrates, such as trimethyl citrate, tripropyl citrate, triisopropylcitrate, tributyl citrate and especially triethyl citrate (Hydagen® CAT,Henkel KGaA, Dusseldorf/FRG), which inhibit enzyme activity and hencereduce odour formation. Further substances that come into considerationas esterase inhibitors are sterol sulfates or phosphates, for examplelanosterol, cholesterol, campesterol, stigmasterol and sitosterolsulfate or phosphate, dicarboxylic acids and esters thereof, for exampleglutaric acid, glutaric acid monoethyl ester, glutaric acid diethylester, adipic acid, adipic acid monoethyl ester, adipic acid diethylester, malonic acid and malonic acid diethyl ester and hydroxycarboxylicacids and esters thereof, for example citric acid, malic acid, tartaricacid or tartaric acid diethyl ester. Antibacterial active ingredientsthat influence the microbial flora and kill or inhibit the growth ofsweat-decomposing bacteria can likewise be present in the preparations(especially in stick preparations). Examples include chitosan,phenoxyethanol and chlorhexidine gluconate.5-Chloro-2-(2,4-dichlorophenoxy)-phenol (Irgasan®, Ciba SpecialtyChemicals Inc.) has also proved especially effective.

[0126] As anti-dandruff agents there may be used, for example,climbazole, octopirox and zinc pyrithione. Customary film formersinclude, for example, chitosan, microcrystalline chitosan, quaternisedchitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetatecopolymers, polymers of quaternary cellulose derivatives containing ahigh proportion of acrylic acid, collagen, hyaluronic acid and saltsthereof and similar compounds. As swelling agents for aqueous phasesthere may be used montmorillonites, clay mineral substances, Pemulen andalso alkyl-modified types of Carbopol (Goodrich). Further suitablepolymers and swelling agents can be found in the review by R. Lochheadin Cosm. Toil. 108, 95 (1993).

[0127] In addition to the primary light-protective substances it is alsopossible to use secondary light-protective substances of the antioxidantkind which interrupt the photochemical reaction chain triggered when UVradiation penetrates the skin or hair. Typical examples of suchantioxidants are amino acids (e.g. glycine, histidine, tyrosine,tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) andderivatives thereof, peptides, such as D,L-carnosine, D-carnosine,L-carnosine and derivatives thereof (e.g. anserine), carotinoids,carotenes (e.g. α-carotene, β-carotene, lycopene) and derivativesthereof, chlorogenic acid and derivatives thereof, lipoic acid andderivatives thereof (e.g. dihydrolipoic acid), aurothioglycose,propylthiouracil and other thiols (e.g. thioredoxin, glutathione,cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl,propyl, amyl, butyl, lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryland glyceryl esters thereof) and also salts thereof, dilaurylthiodipropionate, distearyl thiodipropionate, thiodipropionic acid andderivatives thereof (esters, ethers, peptides, lipids, nucleotides,nucleosides and salts) and also sulfoximine compounds (e.g. buthioninesulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-,hexa-, hepta-thionine sulfoximine) in very small tolerable amounts (e.g.from pmol to μmol/kg), also (metal) chelating agents (e.g. α-hydroxyfatty acids, palmitic acid phytic acid, lactoferrin), α-hydroxy acids(e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bileextracts, bilirubin, biliverdin, EDTA, ECTA and derivatives thereof,unsaturated fatty acids and derivatives thereof (e.g. γ-linolenic acid,linoleic acid, oleic acid), folic acid and derivatives thereof,ubiquinone and ubiquinol and derivatives thereof, vitamin C andderivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate,ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate),vitamin A and derivatives (e.g. vitamin A palmitate) and also coniferylbenzoate of benzoin resin, rutinic acid and derivatives thereof,α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butyl hydroxyanisole, resinous nordihydroguaiareticacid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid andderivatives thereof, mannose and derivatives thereof, superoxidedismutase, N-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]sulfanilicacid (and salts thereof, for example the disodium salts), zinc andderivatives thereof (e.g. ZnO, ZnSO₄), selenium and derivatives thereof(e.g. selenium methionine), stilbene and derivatives thereof (e.g.stilbene oxide, trans-stilbene oxide) and the derivatives suitableaccording to the invention (salts, esters, ethers, sugars, nucleotides,nucleosides, peptides and lipids) of those mentioned active ingredients.HALS (=“Hindered Amine Light Stabilizers”) compounds may also bementioned. The amount of antioxidants present is usually from 0.001 to30% by weight, preferably from 0.01 to 3% by weight, based on the weightof the UV absorber(s).

[0128] To improve the flow behaviour it is also possible to employhydrotropic agents, for example ethanol, isopropyl alcohol or polyols.The polyols that come into consideration for that purpose havepreferably from 2 to 15 carbon atoms and at least two hydroxy groups.

[0129] The polyols may also contain further functional groups,especially amino groups, and/or may be modified with nitrogen. Typicalexamples are as follows:

[0130] glycerol;

[0131] alkylene glycols, for example ethylene glycol, diethylene glycol,propylene glycol, butylene glycol, hexylene glycol and also polyethyleneglycols having an average molecular weight of from 100 to 1000 dalton;

[0132] technical oligoglycerol mixtures having an intrinsic degree ofcondensation of from 1.5 to 10, for example technical diglycerolmixtures having a diglycerol content of from 40 to 50% by weight;

[0133] methylol compounds, such as, especially, trimethylolethane,trimethylolpropane, trimethylolbutane, pentaerythritol anddipentaerythritol;

[0134] lower alkyl-glucosides, especially those having from 1 to 8carbon atoms in the alkyl radical, for example methyl and butylglucoside;

[0135] sugar alcohols having from 5 to 12 carbon atoms, for examplesorbitol or mannitol;

[0136] sugars having from 5 to 12 carbon atoms, for example glucose orsaccharose;

[0137] amino sugars, for example glucamine;

[0138] dialcohol amines, such as diethanolamine or2-amino-1,3-propanediol.

[0139] Suitable preservatives include, for example, phenoxyethanol,formaldehyde solution, Parabens, pentanediol or sorbic acid and thefurther substance classes listed in Schedule 6, Parts A and B of theCosmetics Regulations.

[0140] There may be mentioned as perfume oils mixtures of natural and/orsynthetic aromatic substances. Natural aromatic substances are, forexample, extracts from blossom (lilies, lavender, roses, jasmine,neroli, ylang-ylang), from stems and leaves (geranium, patchouli,petitgrain), from fruit (aniseed, coriander, carraway, juniper), fromfruit peel (bergamot, lemons, oranges), from roots (mace, angelica,celery, cardamom, costus, iris, calmus), from wood (pinewood,sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses(tarragon, lemon grass, sage, thyme), from needles and twigs (spruce,pine, Scots pine, mountain pine), from resins and balsams (galbanum,elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials alsocome into consideration, for example civet and castoreum. Typicalsynthetic aromatic substances are, for example, products of the ester,ether, aldehyde, ketone, alcohol or hydrocarbon type.

[0141] Aromatic substance compounds of the ester type are, for example,benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexylacetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethylacetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate,allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.The ethers include, for example, benzyl ethyl ether; the aldehydesinclude, for example, the linear alkanals having from 8 to 18hydrocarbon atoms, citral, citronellal, citronellyl oxyacetaldehyde,cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; theketones include, for example, the ionones, α-isomethylionone and methylcedryl ketone; the alcohols include, for example, anethol, citronellol,eugenol, isoeugenol, geraniol, linalool, phenyl ethyl alcohol andterpinol; and the hydrocarbons include mainly the terpenes and balsams.It is preferable, however, to use mixtures of various aromaticsubstances that together produce an attractive scent. Ethereal oils ofrelatively low volatility, which are chiefly used as aroma components,are also suitable as perfume oils, e.g. sage oil, camomile oil, cloveoil, melissa oil, oil of cinnamon leaves, lime blossom oil, juniperberry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil andlavandin oil. Preference is given to the use of bergamot oil,dihydromyrcenol, lilial, lyral, citronellol, phenyl ethyl alcohol,α-hexyl cinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde,linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemonoil, tangerine oil, orange oil, allyl amyl glycolate, cyclovertal,lavandin oil, muscatel sage oil, β-damascone, bourbon geranium oil,cyclohexyl salicylate, vertofix coeur, iso-E-Super, Fixolide NP,evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzylacetate, rose oxide, romillat, irotyl and floramat alone or in admixturewith one another.

[0142] There may be used as colourants the substances that are suitableand permitted for cosmetic purposes, as compiled, for example, in thepublication “Kosmetische Färbemittel” of the Farbstoffkommission derDeutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pages81 to 106. The colourants are usually used in concentrations of from0.001 to 0.1% by weight, based on the total mixture.

[0143] Typical examples of bacteria-inhibiting agents are preservativesthat have a specific action against gram-positive bacteria, such as2,4,4′-trichloro-2′-hydroxydiphenyl ether, chlorhexidine(1,6-di(4-chlorophenyl-biguanido)hexane) or TCC(3,4,4′-trichlorocarbanilide). A large number of aromatic substances andethereal oils also have antimicrobial properties.

[0144] Typical examples are the active ingredients eugenol, menthol andthymol in clove oil, mint oil and thyme oil. A natural deodorising agentof interest is the terpene alcohol farnesol(3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in limeblossom oil. Glycerol monolaurate has also proved to be a bacteriostaticagent. The amount of the additional bacteria-inhibiting agents presentis usually from 0.1 to 2% by weight, based on the solids content of thepreparations.

[0145] It is furthermore possible for the cosmetic preparations tocontain, as adjuvants, anti-foams, such as silicones, structurants, suchas maleic acid, solubilisers, such as ethylene glycol, propylene glycol,glycerol or diethylene glycol, opacifiers, such as latex, styrene/PVP orstyrene/acrylamide copolymers, complexing agents, such as EDTA, NTA,β-alaninediacetic acid or phosphonic acids, propellants, such aspropane/butane mixtures, N₂O, dimethyl ether, CO₂, N₂ or air, so-calledcoupler and developer components as oxidation dye precursors, reducingagents, such as thioglycolic acid and derivatives thereof, thiolacticacid, cysteamine, thiomalic acid or α-mercaptoethanesulfonic acid, oroxidising agents, such as hydrogen peroxide, potassium bromate or sodiumbromate.

[0146] There come into consideration as insect repellents, for example,N,N-diethyl-m-toluamide, 1,2-pentanediol or insect repellent 3535;suitable self-tanning agents are, for example, dihydroxyacetone,erythrulose or mixtures of dihydroxyacetone and erythrulose.

[0147] Cosmetic formulations according to the invention are contained ina wide variety of cosmetic preparations. There come into consideration,for example, especially the following preparations:

[0148] skin-care preparations, e.g. skin-washing and cleansingpreparations in the form of tablet-form or liquid soaps, syntheticdetergents or washing pastes,

[0149] bath preparations, e.g. liquid (foam baths, milks, showerpreparations) or solid bath preparations, e.g. bath cubes and bathsalts;

[0150] skin-care preparations, e.g. skin emulsions, multi-emulsions orskin oils;

[0151] cosmetic personal care preparations, e.g. facial make-up in theform of day creams or powder creams, face powder (loose or pressed),rouge or cream make-up, eye-care preparations, e.g. eyeshadowpreparations, mascara, eyeliner, eye creams or eye-fix creams; lip-carepreparations, e.g. lipsticks, lip gloss, lip contour pencils, nail-carepreparations, such as nail varnish, nail varnish removers, nailhardeners or cuticle removers;

[0152] foot-care preparations, e.g. foot baths, foot powders, footcreams or foot balsams, special deodorants and antiperspirants orcallus-removing preparations;

[0153] light-protective preparations, such as sun milks, lotions, creamsor oils, sunblocks or tropicals, pre-tanning preparations or after-sunpreparations;

[0154] skin-tanning preparations, e.g. self-tanning creams;

[0155] depigmenting preparations, e.g. preparations for bleaching theskin or skin-lightening preparations;

[0156] insect-repellents, e.g. insect-repellent oils, lotions, sprays orsticks;

[0157] deodorants, such as deodorant sprays, pump-action sprays,deodorant gels, sticks or roll-ons;

[0158] antiperspirants, e.g. antiperspirant sticks, creams or roll-ons;

[0159] preparations for cleansing and caring for blemished skin, e.g.synthetic detergents (solid or liquid), peeling or scrub preparations orpeeling masks;

[0160] hair-removal preparations in chemical form (depilation), e.g.hair-removing powders, liquid hair-removing preparations, cream- orpaste-form hair-removing preparations, hair-removing preparations in gelform or aerosol foams;

[0161] shaving preparations, e.g. shaving soap, foaming shaving creams,non-foaming shaving creams, foams and gels, preshave preparations fordry shaving, aftershaves or aftershave lotions;

[0162] fragrance preparations, e.g. fragrances (eau de Cologne, eau detoilette, eau de parfum, parfum de toilette, perfume), perfume oils orperfume creams;

[0163] cosmetic hair-treatment preparations, e.g. hair-washingpreparations in the form of shampoos and conditioners, hair-carepreparations, e.g. pretreatment preparations, hair tonics, stylingcreams, styling gels, pomades, hair rinses, treatment packs, intensivehair treatments, hair-structuring preparations, e.g. hair-wavingpreparations for permanent waves (hot wave, mild wave, cold wave),hair-straightening preparations, liquid hair-setting preparations, hairfoams, hairsprays, bleaching preparations, e.g. hydrogen peroxidesolutions, lightening shampoos, bleaching creams, bleaching powders,bleaching pastes or oils, temporary, semi-permanent or permanent haircolourants, preparations containing self-oxidising dyes, or natural haircolourants, such as henna or camomile.

[0164] The final formulations listed may exist in a variety ofpresentation forms, for example:

[0165] in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W orPIT emulsion and all kinds of microemulsions,

[0166] in the form of a gel,

[0167] in the form of an oil, a cream, milk or lotion,

[0168] in the form of a powder, a lacquer, a tablet or make-up,

[0169] in the form of a stick,

[0170] in the form of a spray (spray with propellent gas or pump-actionspray) or an aerosol,

[0171] in the form of a foam, or

[0172] in the form of a paste.

[0173] Of special importance as cosmetic preparations for the skin arelight-protective preparations, such as sun milks, lotions, creams, oils,sunblocks or tropicals, pretanning preparations or after-sunpreparations, also skin-tanning preparations, for example self-tanningcreams. Of particular interest are sun protection creams, sun protectionlotions, sun protection oils, sun protection milk and sun protectionpreparations in the form of a spray.

[0174] Of special importance as cosmetic preparations for the hair arethe above-mentioned preparations for hair treatment, especiallyhair-washing preparations in the form of shampoos, hair conditioners,hair-care preparations, e.g. pretreatment preparations, hair tonics,styling creams, styling gels, pomades, hair rinses, treatment packs,intensive hair treatments, hair-straightening preparations, liquidhair-setting preparations, hair foams and hairsprays. Of specialinterest are hair-washing preparations in the form of shampoos.

[0175] A shampoo has, for example, the following composition: from 0.01to 5% by weight of a UV absorber according to the invention, 12.0% byweight of sodium laureth-2-sulfate, 4.0% by weight of cocamidopropylbetaine, 3.0% by weight of sodium chloride, and water ad 100%.

[0176] For example, especially the following hair-cosmetic formulationsmay be used:

[0177] a₁) spontaneously emulsifying stock formulation, consisting ofthe UV absorber according to the invention, PEG-6-C₁₀oxoalcohol andsorbitan sesquioleate, to which water and any desired quaternaryammonium compound, for example 4% minkamidopropyldimethyl-2-hydroxyethylammonium chloride or Quaternium 80 is added;

[0178] a₂) spontaneously emulsifying stock formulation consisting of theUV absorber according to the invention, tributyl citrate andPEG-20-sorbitan monooleate, to which water and any desired quaternaryammonium compound, for example 4% minkamidopropyldimethyl-2-hydroxyethylammonium chloride or Quaternium 80 is added;

[0179] b) Quat-doped solutions of the UV absorber according to theinvention in butyl triglycol and tributyl citrate;

[0180] c) mixtures or solutions of the UV absorber according to theinvention with n-alkylpyrrolidone.

[0181] The cosmetic preparation according to the invention isdistinguished by excellent protection of human skin against the damagingeffect of sunlight. In the following Examples, percentages relate toweight. The amounts of the triazine derivatives used relate to the puresubstance.

PREPARATION EXAMPLES OF THE NOVEL COMPOUNDS Example 1

[0182] A suspension of 7 g (0.05 mol) of dimedone and 14.8 g (0.1 mol)of orthoformic acid triethyl ester in 15 ml of isobutanol is maintainedat reflux for 2 hours. After cooling to room temperature, 4.6 g (0.025mol) of 2,4-diamino-6-phenyl-1,3,5-triazine and 3 drops oftrifluoromethanesulfonic anhydride are added. The reaction mixture ismaintained at reflux for 20 hours and then cooled to room temperature.The resulting crude product is filtered off. The colourless product isobtained by column chromatography (silica gel) using a 9:1 mixture ofdichloromethane and methanol as eluant and is dried at 60° C. in vacuo.

[0183] Yield: 1 g (8% of theory).

[0184] λ_(max)=320 nm; ε=50 970, E (=extinction value) (1%, 1 cm)=1045.

[0185] γ_(max)=224 nm; ε=35 699, E (1%, 1 cm)=732.

Example 2

[0186] 0.1 ml of trifluoromethanesulfonic anhydride is added, at 90° C.,to a solution of 7.5 g (0.05 mol) of orthoformic acid triethyl ester in50 ml of isobutanol. 2.3 g (0.0125 mol) of2,2-diamino-6-phenyl-1,3,5-triazine are then introduced in portions inthe course of 1.5 hours. The resulting solution is stirred for 30minutes at 100° C. After the addition of 2.3 g (0.025 mol) ofacetylacetone, the reaction mixture is maintained at reflux for 4 hours.After cooling to room temperature, the suspension is filtered. Thefilter cake is recrystallised from ethyl acetate and dried in vacuo at70° C. Yield: 1.3 g (26% of theory).

[0187] λ_(max)=322 nm; ε=42 906, E (1%, 1 cm)=1053 (in ethanol).

Example 3

[0188] 7.2 g (0.05 mol) of malonic acid cyclic isopropylidene ester,14.8 g (0.1 mol) of orthoformic acid triethyl ester and 4.6 g (0.025mol) of diaminophenyltriazine are mixed in 150 ml of toluene and thenmaintained at reflux for 1 hour. In the course of 2 hours, 2.5 g ofphosphoryl chloride are added dropwise and the reaction mixture isrefluxed for a further 2 hours. After cooling to room temperature, 100ml of water and 100 ml of ethyl acetate are added. The organic phase isseparated off and heated for 30 minutes at 40-50° C. together with 5 gof sodium sulfate and 5 g of Tonsil. After filtration of the mixturewhile it is still warm, the filtrate is concentrated to dryness byevaporation. Subsequent column chromatography (silica gel) using a 7:3mixture of toluene and acetone yields the pure product, which is driedin vacuo at 80° C. Yield: 5 g (40% of theory).

[0189] λ_(max)=332 nm; ε=68 068, E (1%, 1 cm)=1374 (in dioxane).

Example 4

[0190] In a sulfonating flask equipped with a reflux condensor and acalcium chloride drying tube, 4.78 g (0.025 mol) of2,4-diamino-6-phenyl-1,3,5-triazine, 9.96 g (0.075 mol) of ethylaceto-acetate, 8.12 g (0.075 mol) of orthoformic acid trimethyl esterand 1.03 g (0.006 mol) of copper(II) chloride dihydrate are mixed in 50ml of dimethylacetamide and stirred for 3 hours at 70° C. After coolingto room temperature, the reaction mixture is stirred into 200 ml of 10%sodium sulfate solution. The precipitate that forms is filtered off,washed neutral with water and recrystallised from ethanol. The productis dried in vacuo at 60° C.

[0191] Yield: 4.1 g (35% of theory).

[0192] Yield: 4.1 g (35% of theory)

[0193] λ_(max)=319 nm; ε=45 969, E (1%, 1 cm)=983 (in ethanol).

Example 5

[0194] 3.22 g (0.025 mol) of melamine, 14.94 g (0.1125 mol) of ethylacetoacetate, 12.18 g (0.1125 mol) of orthoformic acid trimethyl esterand 1.03 g (0.006 mol) of copper(II) chloride dihydrate are stirred in50 ml of N-methylpyrrolidone for 4 hours at 80° C. The cold reactionmixture is added to 400 ml of 5% aqueous sodium sulfate solution. Theresulting precipitate is filtered off, washed with water andrecrystallised from ethanol. The product is dried in vacuo at 60° C.Yield: 6.5 g (48% of theory).

[0195] λ_(max)=325 nm; ε=790448, E (1%, 1 cm)=1350 (in dioxane).

Example 6

[0196] 3.22 g (0.025 mol) of melamine, 16.60 g (0.113 mol) of malonicacid cyclic isopropylidene ester, 17.09 g (0.113 mol) of orthoformicacid triethyl ester and 1.03 g (0.006 mol) of copper(II) chloridedihydrate are stirred in 50 ml of N-methylpyrrolidone for 6 hours at 80°C. The cold reaction mixture is added to 400 ml of 5% aqueous sodiumsulfate solution. The resulting precipitate is filtered off, washed withwater and copious amounts of ethanol. The product is dried in vacuo at60° C. Yield: 6.2 g (42% of theory).

[0197] λ_(max)=326 nm; ε=61 956, E (1%, 1 cm)=1053 (in dioxane).

Example 6 Parallel Syntheses of the Compounds of the General Formula

[0198]

[0199] General Procedure:

[0200] 2,4-Diamino-6-phenyl-1,3,5-triazine (0.0013 mol, 0.24 g) isdissolved in N-methylpyrrolidone (1.15 ml). Orthoformic acid trimethylester (0.0038 mol, 0.42 ml), copper chloride dihydrate solution (0.0013mol. 0.22 g in 0.5 ml of NMP) and the appropriate ketone (0.0038 moldissolved in 2 ml of NMP) are added to the solution. The reactionmixture is shaken for 4 hours at 70° C. The crude product isprecipitated by the addition of 10 ml of 10% aqueous sodium sulfatesolution, and the precipitate is then filtered off and washed withcopious amounts of ethanol. Subsequent column chromatography (Nucleosil5C18) using a mixture of acetonitrile and water yields the pure product.

Example 7 Parallel Syntheses of the Compounds of Formula

[0201]

[0202] General Procedure:

[0203] Melamine (0.0013 mol, 0.17 g) is dissolved in N-methylpyrrolidone(1.42 ml). Orthoformic acid trimethyl ester (0.0057 mol, 0.59 ml),copper chloride dihydrate solution (0.0013 mol. 0.22 g in 0.5 ml of NMP)and the appropriate ketone (0.0057 mol dissolved in 2 ml of NMP) areadded to the solution. The reaction mixture is shaken for 4 hours at 80°C. The crude product is precipitated by the addition of 10 ml of 10%aqueous sodium sulfate solution, and the precipitate is then filteredoff and washed with copious amounts of ethanol. Subsequent columnchromatography (Nucleosil 5C18)) using a mixture of acetonitrile andwater yields the pure product.

Example 8 Parallel Syntheses of the Compounds of Formula

[0204]

[0205] General Procedure:

[0206] 2,4-Diamino-6-p-methoxyphenyl-1,3,5-triazine (0.0005 mol, 0.11 g)is dissolved in N-methylpyrrolidone (0.6 ml). Orthoformic acid trimethylester (0.0013 mol, 0.14 g), copper chloride dihydrate solution (0.0013mol, 0.22 g in 0.5 ml of NMP) and the appropriate ketone (0.0005 moldissolved in 0.23 ml of NMP) are added to the solution. The reactionmixture is shaken for 4 hours at 80° C. The crude product isprecipitated by the addition of 10 ml of 10% aqueous sodium sulfatesolution, and the precipitate is then filtered off and washed withcopious amounts of ethanol. Subsequent column chromatography (Nucleosil5C18)) using a mixture of acetonitrile and water yields the pureproduct.

Example 9 Parallel Syntheses of the Compounds of Formula

[0207]

[0208] General Procedure:

[0209] 2,4-Diamino-6-methyl-1,3,5-triazine (0.0013 mol, 0.16 g) isdissolved in N-methylpyrrolidone (1.5 ml). Orthoformic acid trimethylester (0.0038 mol, 0.42 ml), copper chloride dihydrate solution (0.0013mol, 0.22 g in 0.5 ml of NMP) and the appropriate ketone (0.0038 moldissolved in 2 ml of NMP) are added to the solution. The reactionmixture is shaken for 4 hours at 70° C. The crude product isprecipitated by the addition of 10 ml of 10% aqueous sodium sulfatesolution, and the precipitate is then filtered off and washed withcopious amounts of ethanol. Subsequent column chromatography (Nucleosil5C18) using a mixture of acetonitrile and water yields the pure product.

APPLICATION EXAMPLES Example 10 Sun Protection Lotion

[0210] INCI-Name % w/w Part A Glyceryl Stearate (and) PEG-100 Stearate5.00 Stearyl Alcohol 1.00 Tripalmitin 0.70 Dimethicone 2.00 C₁₂₋₁₅ AlkylBenzoate 5.00 Isopropyl Palmitate 5.00 Ethylhexyl Methoxycinnamate 3.00Part B Water qs to 100 Polysorbate 60 0.50 Glycerin 3.00 Part C Water10.00 Compound of formula 101 or 102 or 103 or 8.00 104 or 105 or 106Part D Phenoxyethanol (and) Methylparaben (and) 0.70 Ethylparaben (and)Butylparaben (and) Propylparaben (and) Isobutylparaben Steareth-10 AllylEther/Acrylates Copolymer 1.50 Part E Water (and) Sodium Hydroxide qsPart F Fragrance qs

[0211] This emulsion is easy to spread with good absorption properties.

[0212] Manufacturing Instruction:

[0213] Heat part A and B separately up to 75° C.; part C to 60° C.Afterwards pour part B into part A under stirring. Homogenize with anUltra Turrax for 30 sec. at 11000 rpm and incorporate part C. Let cooldown to 40° C. and add part D. At room temperature adjust the pH-valuewith Sodium Hydroxide between 6.30 and 6.70 and add part F.

Example 11 Sprayable Sunscreen Lotion

[0214] INCI-Name % w/w Part A Potassium Cetyl Phosphate 0.20Isohexadecane 7.00 VP/Eicosene Copolymer 1.50 Di-C₁₂₋₁₃ Alkyl Tartrate6.00 Ethylhexyl Triazone 2.50 C₁₂₋₁5 Alkyl Benzoate 4.50 Part B Water qsto 100 Sorbeth-30 2.00 Sorbitan Stearate (and) Sucrose Cocoate 4.00Titanium Dioxide (and) Alumina (and) Silica (and) 2.50 SodiumPolyacrylate Part C Water 30.00 Compound of formula 101 or 102 or 103 or104 on 12.00 105 or 106 Part D Phenoxyethanol (and) Methylparaben (and)0.70 Ethylparaben (and) Butylparaben (and) Propylparaben (and)Isobutylparaben Part E Water (and) Citric Acid qs

[0215] This emulsion contains a combination of insoluble UV-absorber.The choice of emollients provides quick absorption and smooth after skinfeeling.

[0216] Manufacturing Instruction:

[0217] Heat part A and part B separately up to 80° C.; part C to 50° C.Pour part B into part A and homogenize with an Ultra Turrax for 1 minuteby 11000 rpm. After cooling down to 50° C. add part C under continuousstirring. At 40° C. incorporate part D and homogenize again for 10 sec.by 11000 rpm. Adjust the pH with part E.

Example 12 Sunscreen Lotion, Water Resistant

[0218] INCI-Name % w/w Part A Cetearyl Alcohol (and) Dicetyl Phosphate(and) 4.00 Ceteth-10 Phosphate C₁₂₋₁₅ Alkyl Benzoate 2.00 DicaprylylEther 3.00 Ethoxydiglycol Oleate 2.00 Stearic Acid 1.00 EthylhexylMethoxycinnamate 3.00 Sodium Acrylates Copolymer (and) Glycine Soja(and) 0.30 PPG-1 Trideceth-6 Squalane 3.50 VP/Eicosene Copolymer 2.00Part B Water qs to 100 Compound of formula 101 or 102 or 103 or 104 5.00or 105 or 106 Part C Diazolidinyl Urea (and) Iodopropynyl Butylcarbamate0.15 Propylene Glycol 2.50 Water 10.00 Part D Cyclopentasiloxane (and)Dimethiconol 2.00 Ethoxydiglycol 5.00 Cyclopentasiloxane (and)Dimethicone/Vinyl 2.00 Dimethicone Crosspolymer Part E Aqua (and) SodiumHydroxide qs Part F Fragrance qs

[0219] O/W emulsion with a soft touch and good rub in properties.

[0220] Manufacturing Instruction:

[0221] Heat part A and part B separately up to 75° C. Pour part B intopart A under progressive stirring speed. Below 65° C. add separately theingredients of part D. Let cool down to 55° C. under moderate stirringand add part C. Less than 35° C. check and adjust the pH with SodiumHydroxide and homogenize with an Ultra Turrax for 30 sec. at 11000 rpm.At room temperature add part F.

Example 13

[0222] INCI-Name % w/w Part A Potassium Cetyl Phosphate 2.00 TricontanylPVP 1.00 Caprylic/Capric Triglyceride 5.00 C₁₂₋₁₅ Alkyl Benzoate 5.00Cetearyl Isononanoate 5.00 Glyceryl Stearate 3.00 Cetyl Alcohol 1.00Dimethicone 0.10 Ethylhexyl Methoxycinnamate 5.00 Part B Water qs to 100Glycerin 3.00 Part C Steareth-10 Allyl Ether/Acrylates Copolymer 0.50Part D Compound of formula 101 or 102 or 103 or 104 8.00 or 105 or 106Part E Phenoxyethanol (and) Methylparaben 1.00 (and) Ethylparaben (and)Butylparaben (and) Propylparaben (and) Isobutylparaben Part F Water(and) Sodium Hydroxide qs to pH 7.00 Part G Fragrance qs

[0223] This emulsion is smooth and spreads easily. The choice of mainlylight emollients gives the lotion a light and non-tacky skin feeling.

[0224] Manufacturing Instruction:

[0225] Heat part A and part B separately up to 80° C. Pour part B intopart A under moderate stirring. Homogenize with an Ultra Turrax at 11000rpm for 1 minute. Let cool down to 70° C. and add part C under stirring.Cool further down to 50° C. and incorporate TINOSORB® M very slowly. At40° C. add part E. At room temperature adjust the pH with part F to 7.00and add part G.

Example 14 O/W Emulsion Water Resistant

[0226] INCI-Name % w/w Part A Cetearyl Alcohol (and) Dicetyl Phosphate4.00 (and) Ceteth-10 Phosphate C₁₂₋₁₅ Alkyl Benzoate 2.00 DicaprylylEther 3.00 Ethoxydiglycol Oleate 2.00 Stearic Acid 1.00 EthylhexylMethoxycinnamate 3.00 Sodium Acrylates Copolymer (and) Glycine Soja 0.30(and) PPG-1 Trideceth-6 Squalane 3.50 VP/Eicosene Copolymer 2.00 Part BWater qs to 100 Compound of formula 101 or 102 or 103 or 104 on 5.00 105or 106 Part C Diazolidinyl Urea (and) Iodopropynyl 0.15 ButylcarbamatePropylene Glycol 2.50 Water 10.00 Part D Cyclopentasiloxane (and)Dimethiconol 2.00 Ethoxydiglycol 5.00 Cyclopentasiloxane (and)Dimethicone/Vinyl 2.00 Dimethicone Crosspolymer Part E Aqua (and) SodiumHydroxide qs Part F Fragrance qs

[0227] O/W emulsion with a soft touch and good rub in properties.

[0228] Manufacturing Instruction:

[0229] Heat part A and part B separately up to 75° C. Pour part B intopart A under progressive stirring speed. Below 65° C. add separately theingredients of part D. Let cool down to 55° C. under moderate stirringand add part C. Less than 35° C. check and adjust the pH with SodiumHydroxide and homogenize with an Ultra Turrax for 30 sec. at 11000 rpm.At room temperature add part F.

Example 14 Sun Protection Lotion, O/W Type

[0230] INCI-Name % w/w Part A Potassium Cetyl Phosphate 2.00 TricontanylPVP 1.00 Caprylic/Capric Triglyceride 5.00 C₁₂₋₁5 Alkyl Benzoate 5.00Cetearyl Isononanoate 5.00 Glyceryl Stearate 3.00 Cetyl Alcohol 1.00Dimethicone 0.10 Ethylhexyl Methoxycinnamate 5.00 Part B Water qs to 100Glycerin 3.00 Part C Steareth-10 Allyl Ether/Acrylates Copolymer 0.50Part D Compound of formula 101 or 102 or 103 or 104 20.00 or 105 or 106Part E Phenoxyethanol (and) Methylparaben 1.00 (and) Ethylparaben (and)Butylparaben (and) Propylparaben (and) Isobutylparaben Part F Water(and) Sodium Hydroxide qs to pH 7.00 Part G Fragrance qs

[0231] This emulsion is smooth and spreads easily.

[0232] Manufacturing Instruction:

[0233] Heat part A and part B separately up to 80° C. Pour part B intopart A under moderate stirring. Homogenize with an Ultra Turrax at 11000rpm for 1 minute. Let cool down to 70° C. and add part C under stirring.Cool further down to 50° C. and incorporate TINOSORB® M very slowly. At40° C. add part E. At room temperature adjust the pH with part F to 7.00and add part G.

1. A compound of formula

wherein R₁ is a C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₆-C₁₀aryl orC₆-C₁₀heteroaryl radical each unsubstituted or mono- or poly-substitutedby hydroxy, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, amino, C₁-C₅monoalkyl-amino or bydi-C₁-C₅alkylamino; C₅-C₇cycloalkyl or C₅-C₇cycloalkenyl eachunsubstituted or substituted by C₁-C₅alkyl; —OR′; or —NR′R″; R₂ ishydrogen; a C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₆-C₁₀aryl or C₆-C₁₀heteroarylradical each unsubstituted or mono- or poly-substituted by hydroxy,C₁-C₁₈alkoxy, cyano, amino, C₁-C₅monoalkylamino or bydi-C₁-C₅alkylamino; —OR′; or —NR′R″; or R₁ and R₂ together form a 5- to7-membered carbocyclic or heterocyclic ring; A is C₁-C₅alkyl; anunsubstituted or hydroxy-, C₁-C₁₈alkyl- or C₁-C₁₈alkoxy-substitutedC₆-C₁₀aryl or heteroaryl radical; or a radical of formula

R′ and R″ are each independently of the other hydrogen; unsubstituted ormono- or poly-hydroxy-, halo-, C₁-C18alkyl-, C₁-C₁₈alkoxy-, amino- orquaternary ammonium group-substituted C₁-C₁₈alkyl, C₅-C₇cycloalkyl orphenyl; R₃ is hydrogen; or C₁-C₆alkyl; and n is 0 or
 1. 2. A compoundaccording to claim 1, wherein R₁ and R₂ are each independently of theother C₁-C₁₈alkyl or phenyl each unsubstituted or substituted byC₁-C₅alkyl, hydroxy or by C₁-C₅alkoxy; —OR′; or —NR′R″; or R₁ and R₂together form a 5- to 7-membered carbocyclic or heterocyclic ring.
 3. Acompound according to claim 1, wherein R₁ is C₁-C₅alkyl; C₁-C₅alkoxy; orunsubstituted or C₁-C₅alkyl-, hydroxy- or C₁-C₅alkoxy-substitutedphenyl.
 4. A compound according to claim 1, wherein R₂ is hydrogen;C₁-C₅alkyl; C₁-C₅alkoxy; unsubstituted or hydroxy-, C₁-C₅alkyl- orC₁-C₅-alkoxy-substituted phenyl; and n is
 1. 5. A compound according toclaim 1, wherein R₁ and R₂ together are a —(CH₂)₂₋₅— radical that is notfurther substituted or is substituted by one or more C₁-C₅alkyl groupsand is uninterrupted or interrupted by one or two —O— and/or —NH— groupsand/or


6. A compound according to claim 5, wherein R₁ and R₂ together are a

radical; and R₅ is hydrogen; or C₁-C₅alkyl.
 7. A compound according toclaim 1, wherein A is amino; phenyl; or C₁-C₅alkoxyphenyl.
 8. A compoundaccording to claim 1, wherein R₃ is hydrogen.
 9. A process for thepreparation of a triazine derivative of formula (1) according to claim1, wherein a diaminotriazine compound of formula

is reacted with a compound of formula

to form a compound of formula (1), wherein R₁ is C₁-C₅alkyl and R and R′are as defined for formula (1) in claim 1, to form a compound of formula(1).
 10. A method for the protection of human and animal hair and skinagainst the damaging effect of UV radiation, which comprises contactingsaid hair or skin with an effective protective amount of a triazinederivative of formula (1) according to claim
 1. 11. A method accordingto claim 10, wherein the triazine derivative of formula (1) is presentin micronised form.
 12. A cosmetic preparation comprising at least onecompound of formula (1) according to claim 1 together with acosmetically tolerable carrier or adjuvant.
 13. A preparation accordingto claim 12 that comprises further UV protective substances.